Rubber-metal laminate and gasket

ABSTRACT

A rubber-metal laminate that includes a metal member; and a rubber layer provided on the metal member, wherein the rubber layer has a 100%-modulus value in accordance with JIS K6251 of 8.5 MPa or more and a thickness of 80 μm or more. A gasket that includes the rubber-metal laminate.

TECHNICAL FIELD

The present invention relates to a rubber-metal laminate and a gasket.

BACKGROUND ART

A metal gasket that is sandwiched between two members, such as acylinder head and cylinder block in an engine, for sealing has beenconventionally proposed (for example, see Patent Literature 1). Thismetal gasket includes a rubber-metal laminate including a metalsubstrate and a rubber layer provided on both main surfaces of the metalsubstrate. The metal gasket described in Patent Literature 1 seals a gapbetween the cylinder head and the cylinder block, which are sealingtarget members, with fastening of the rubber-metal laminate between thecylinder head and the cylinder block.

In the metal gasket described in Patent Literature 1, the rubber-metallaminate is fastened between metal members such as the cylinder head andthe cylinder block, and thereby a strong compressive stress is appliedto the rubber-metal laminate in use. With such a rubber-metal laminate,the rubber layer is deformed by application of the compressive stress inuse, which may cause the rubber to protrude from the rubber-metallaminate, and fail to yield desired functions.

To inhibit the protrusion of the rubber due to the deformation of therubber layer, it is effective to blend a filler such as carbon black andsilica into the rubber layer to increase a hardness of the rubber layer.However, increase in the hardness of the rubber layer may deterioratesealability of the sealing target members with the rubber layer. Toinhibit the protrusion of the rubber, it is investigated that a blendingamount of sulfur used as a crosslinking agent of a rubber layercomposition is increased to increase a crosslinking density of therubber layer. Unfortunately, even when the crosslinking density of therubber layer is increased, a remarkable effect of inhibiting theprotrusion of the rubber is not expected. As above, in the conventionalrubber-metal laminates, the protrusion of the rubber may not besufficiently inhibited only with increasing the hardness, and arelationship between the property and protrusion of the rubber has notbeen found actually.

DOCUMENT LIST Patent Literature

-   Patent Literature 1: Japanese Patent Application Publication No.    2003-130224

SUMMARY OF INVENTION Technical Problem

The present invention has been made considering the above circumstance,and it is an object of the present invention to provide a rubber-metallaminate and gasket that can prevent the protrusion of the rubber layerupon application of the compressive stress and that have excellentsealability of the sealing target members.

Solution to Problem

A rubber-metal laminate according to an embodiment of the presentinvention comprises: a metal member; and a rubber layer provided on themetal member, wherein the rubber layer has a 100%-modulus value inaccordance with JIS K6251 of 8.5 MPa or more and a thickness of 80 μm ormore.

In an aspect of the present invention, the rubber layer has a100%-modulus value in accordance with JIS K6251 of 10.5 MPa or more.

In an aspect of the present invention, the rubber layer has anelongation value in accordance with JIS K6251 of 100% or more.

In an aspect of the present invention, the rubber layer has a thicknessof 200 μm or less.

In an aspect of the present invention, the rubber layer contains 30 mass% or more of carbon black based on a total mass of the rubber layer.

In an aspect of the present invention, the metal member and the rubberlayer are bonded with at least one adhesive selected from the groupconsisting of a phenolic resin and an epoxy resin disposed therebetween.

In an aspect of the present invention, the rubber layer contains anitrile rubber.

A gasket according to an aspect of the present invention comprises therubber-metal laminate.

Effects of Invention

According to the present invention, the rubber-metal laminate and gasketthat can prevent the protrusion of the rubber layer upon application ofthe compressive stress and that have excellent sealability of thesealing target members can be achieved.

DESCRIPTION OF EMBODIMENTS

Hereinafter, embodiments of the present invention will be described indetail. The rubber-metal laminate according to an embodiment of thepresent invention is preferably used as a sealing member such as agasket. The metal laminate according to the present embodiment includesa metal member and a rubber layer provided on at least one main surfaceof the metal member. The rubber layer has a 100%-modulus value of 8.5MPa or more and a thickness of 80 μm or more. Since the 100%-modulusvalue of the rubber is 8.5 MPa or more and the thickness is 80 μm ormore, an elastic modulus of the rubber layer appropriately increases.According to this rubber layer, the rubber-metal laminate can preventdeterioration of sealability and achieve an elastic modulus required forthe rubber layer compared with a case where the hardness of the rubberlayer is increased with a filler. As a result, even when the compressivestress is applied to the rubber-metal laminate, the protrusion of therubber layer from the rubber-metal laminate can be further prevented,and the rubber-metal laminate having excellent sealability of thesealing target members can be achieved. Hereinafter, each component ofthe rubber-metal laminate according to the present embodiment will bedescribed in detail.

(Metal Member)

As the metal member, a metal sheet such as, for example, iron, stainlesssteel, aluminum, magnesium, zinc-plated steel, and copper is used. Asiron, a cold rolled steel sheet (SPCC: Steel Plate Cold Commercial), ahigh-tensile steel sheet, a soft steel sheet, and the like are used, forexample. As stainless steel, ferrite-type, martensite-type,austenite-type stainless steel sheet, and the like can be used, forexample. As specific examples of stainless steel, SUS304, SUS301,SUS301H, SUS430, and the like can be mentioned, for example. Asaluminum, an aluminum sheet, an aluminum die-cast sheet, and the likeare used.

It is preferable that the metal member be used in a state where thesurface is defatted with an alkali defatting treatment or the like. Themetal member is used with the metal surface roughened by shot blasting,Scotch-Brite®, hairline, dull-finish and the like, if necessary.

In the metal member, it is preferable that an adhesion surface with theadhesive be subjected to a substrate treatment (surface treatment). Thesubstrate treatment is not particularly limited, and known substratetreatments can be used. For the substrate treatment when an ironmaterial and a stainless steel material such as a cold rolled steelsheet and a high-tensile steel sheet are used as the metal member, achemical treatment method using various chemical treating agent, andvarious plating methods such as an electrical plating and a hot-dipplating with a metal such as zinc are preferable. As the chemicaltreating agent for the metal member, for example, phosphate treatingagents such as a zinc phosphate treating agent and an iron phosphatetreating agent, and coating-type chromate treating agent can bementioned. As the chemical treating agent, a chromium-free chemicaltreating agent containing substantially no chromium is preferable fromthe viewpoint of environmental protection.

The substrate treatment for the metal member with the chemical treatingagent is performed by contacting the chemical treating agent with themetal member with known liquid-contacting methods such as atomizing,spraying, immersing, brush coating, and a roll coater. In a case of areactive chemical treating agent, it is needed that a time andtemperature required for the reaction are prepared.

A thickness of the metal member is appropriately set according to a useof the rubber-metal laminate. When the rubber-metal laminate is used fora sealing material such as a gasket, it is preferable that the thicknessof the metal member be 100 μm or more and 2000 μm or less, it is morepreferable that it be 200 μm or more and 1000 μm or less, and it isfurther preferable that it be 300 μm or more and 500 μm or less, forexample.

In the rubber-metal laminate, it is preferable that a primer layer beformed on the metal member in addition to the substrate treatment orinstead of the substrate treatment. By performing the substratetreatment or providing the primer layer, adhesiveness between the rubberlayer and the metal member in the rubber-metal laminate is improved, andheat resistance and water resistance of the rubber-metal laminate can beremarkably improved. In addition, by performing the substrate treatmentor forming the primer layer in the rubber-metal laminate, therubber-metal laminate can be preferably used as a gasket that is alaminated complex metal in which the rubber-metal laminate is laminatedwith another metal sheet and the like.

The primer layer can be provided by: a silicon compound; compounds ofmetals such as titanium, zirconium, vanadium, aluminum, molybdenum,tungsten, manganese, zinc, and cerium, and inorganic compounds such asan oxide thereof; and organic compounds such as a silicone resin, aphenolic resin, an epoxy resin, and polyurethane. The primer layer canbe provided by using commonly commercially available primer solutions,and other primer solutions of various known art.

The primer layer is provided by a primer solution in which a rawmaterial containing the above various inorganic compounds or organiccompounds is dissolved or dispersed in an organic solvent or an aqueoussolvent. As a usable organic solvent, alcohols such as methanol,ethanol, and isopropyl alcohol, ketones such as acetone and methyl ethylketone, and the like can be mentioned, for example. The primer solutionmay be prepared as an aqueous solution using an aqueous solvent as longas it maintains the liquid stability.

The obtained primer solution is applied onto the metal member by using aspray, immersion, a brush, a roll coater, and the like. Then, the primerlayer is provided by drying the primer solution applied onto the metalmember at room temperature or with warm blowing, or by baking treatment.

(Adhesive)

The adhesive bonds the rubber layer and the metal member. As theadhesive, commonly commercially available adhesives such as a phenolicresin, an epoxy resin, a polyurethane resin, and a silane are used.These adhesives can be appropriately selected according to use of therubber-metal laminate.

In the rubber-metal laminate, it is preferable that the metal member andthe rubber layer be bonded with at least one adhesive selected from thegroup consisting of a phenolic resin and an epoxy resin disposedtherebetween. Since the adhesiveness between the metal member and therubber layer in the rubber-metal laminate is improved by this adhesive,the protrusion of the rubber layer from the rubber-metal laminate uponapplication of the compressive stress can be further prevented, and thesealability of the sealing target members can be further improved.

As the phenolic resin, a novolac-type phenolic resin and a resol-typephenolic resin are used, for example. The novolac-type phenolic resinand the resol-type phenolic resin may be used singly, or may be used incombination of two or more thereof. As the adhesive, an adhesivecontaining two phenolic resins of the novolac-type phenolic resin andthe resol-type phenolic resin and an unvulcanized nitrile rubber may beused.

As the novolac-type phenolic resin, a product obtained with acondensation reaction between phenols and formaldehyde in the presenceof an acid catalyst is used. As the phenols, ones having two or threesubstitutable hydrogen atoms at at least one of o-position andp-position with respect to a phenolic hydroxy group of, for example,phenol, p-cresol, m-cresol, p-tert-butylphenol, p-phenylphenol, andbisphenol A are used. These phenolic resins may be used singly, or maybe used in combination of two or more thereof. As the acid catalyst,oxalic acid, hydrochloric acid, maleic acid, and the like are used, forexample. Among them, it is preferable that the novolac-type phenolicresin have a melting point of 80° C. or higher and 150° C. or lower, andit is more preferable that it be obtained by using m-cresol andformaldehyde and have a melting point of 120° C. or higher, from theviewpoint of improvement in the adhesiveness between the metal memberand the rubber layer.

As the resol-type phenolic resin, a product obtained with a condensationreaction between phenols and formaldehyde in the presence of a basecatalyst is used. As the phenols, ones having two or three substitutablehydrogen atoms at at least one of o-position and p-position with respectto a phenolic hydroxy group of, for example, phenol, p-cresol, m-cresol,p-tert-butylphenol, p-phenylphenol, and bisphenol A are used. Thesephenolic resins may be used singly, or may be used in combination of twoor more thereof. As the base catalyst, ammonia, alkali metal hydroxidessuch as sodium hydroxide, magnesium hydroxide, and sodium carbonate, andthe like are used, for example.

As the epoxy resin, a bisphenol A-type, cresol-novolac-type,biphenyl-type, and brominated epoxy resins can be mentioned. These epoxyresins may be used singly, or may be used in combination of two or morethereof. Among these epoxy resins, the bisphenol A-type epoxy resin andthe cresol-novolac-epoxy resin are preferable from the viewpoint of easyavailability of a commercial product and the viewpoint of excellence inheat resistance. As the bisphenol A-type epoxy resin, commercialproducts such as “EPICLON® 860”, “EPICLON® 1055”, “EPICLON® 2050”,“EPICLON® 3050”, “EPICLON® 4050”, “EPICLON® 7050”, and “EPICLON®HM-091”, which are trade names of DIC Corporation, may be used, forexample. As the commercial product of the cresol-novolac-type epoxyresin, commercial products such as “EPICLON®N-660”, “EPICLON®N-670”,“EPICLON®N-680”, and “EPICLON®N-690”, which are trade names of DICCorporation, may be used, for example.

The above various adhesives are dissolved in an organic solvent to beused as a solution. As the organic solvent, ketones such as methyl ethylketone and methyl isobutyl ketone, aromatic hydrocarbons such as tolueneand xylene, and the like are used, for example. These organic solventsmay be used singly, or may be used in combination of two or morethereof.

It is preferable that the adhesive be blended at a proportion of, forexample, 10 parts by mass or more and 1000 parts by mass or less of theresol-type phenolic resin per 100 parts by mass of the novolac-typephenolic resin, and it is more preferable that it be blended at aproportion of 60 parts by mass or more and 400 parts by mass or less. Byblending the adhesive at a proportion of 1000 parts by mass or less ofthe resol-type phenolic resin per 100 parts by mass of the novolac-typephenolic resin, deterioration of the adhesiveness of the rubber layercan be prevented. In addition, by setting the proportion to 10 parts bymass or more, deterioration of the adhesiveness to the surface of themetal member can be prevented.

It is preferable that the adhesive be provided on the metal member onwhich the primer layer is formed from the viewpoint of improvement inthe adhesiveness between the metal member and the rubber layer. Theadhesive layer may be provided as a single layer, and may be provided asa multilayer. The adhesive layer may be provided as a multistagestructure by forming a phenolic adhesive layer including an organometalcompound on the primer layer provided on the metal member, and then, onthe adhesive layer providing an additional phenolic adhesive layer. Byforming such an adhesive layer of the multistage structure, theadhesiveness between the primer layer and the rubber layer can befurther strengthened.

The adhesive is prepared as an adhesive solution at a solid-contentconcentration of 1 mass % or more and 10 mass % or less by usingketone-type organic solvents such as acetone, methyl ethyl ketone,methyl isobutyl ketone, and a mixed solvent thereof. The solution of theadhesive is applied onto the metal member, and then subjected to dryingand baking treatment under a condition at 100° C. or higher and 250° C.or lower for approximately 1 minute or longer and 30 minutes or shorter,to be formed into an adhesive layer. It is preferable that the amount ofthe adhesive applied be such that the coating mass after drying andbaking treatment following application is within a range of 50 mg/m² ormore and 2000 mg/m² or less. It is preferable that the adhesive beapplied so that the thickness of the adhesive layer after the drying is0.5 μm or more and 5 μm or less.

(Rubber Layer)

In the rubber-metal laminate according to the preset embodiment, therubber layer has a 100%-modulus value in accordance with JIS K6251 of8.5 MPa or more. According to this rubber layer, the rubber layer has anappropriate elastic modulus even when a high compressive stress isapplied to the rubber-metal laminate, and the protrusion of the rubberlayer from the rubber-metal laminate can be inhibited. Therefore, thesealability of the sealing target members is improved. In addition,since the rubber-metal laminate has the appropriate elastic moduluswithout increasing the hardness of the rubber layer, the sealability ofthe sealing target members is improved with preventing deterioration ofthe sealability and maintaining flexibility of the rubber.

It is more preferable that the 100%-modulus value of the rubber layer be10.5 MPa or more, and it is further preferable that it be 12 MPa or morefrom the viewpoint of further improvement in the above effect, and it ispreferable that it be 30 MPa or less, it is more preferable that it be25 MPa or less, and it is further preferable that it be 20 MPa or less.With the 100%-modulus value of 10.5 MPa or more, in the rubber-metallaminate, deterioration of the sealability can be prevented, and theelastic modulus required for the rubber layer can be sufficientlymaintained. As a result, in the rubber-metal laminate, the protrusion ofthe rubber layer from the rubber-metal laminate can be further preventedeven when the compressive stress is applied to the rubber-metallaminate. Therefore, the sealability of the sealing target members isfurther improved.

In the rubber-metal laminate according to the present embodiment, it ispreferable that the rubber layer have an elongation value in accordancewith JIS K6251 of 100% or more. According to this rubber layer, sincethe elongation value of the rubber layer is within an appropriate range,the protrusion of the rubber layer from the rubber-metal laminate can befurther prevented even when the compressive stress is applied to therubber-metal laminate. Therefore, the sealability of the sealing targetmembers is further improved. It is more preferable that the elongationvalue of the rubber layer be 140% or more, and it is further preferablethat it be 170% or more from the viewpoint of further improvement in theabove effect, and it is preferable that it be 300% or less, it is morepreferable that it be 240% or less, and further preferable that it be200% or less.

In the rubber-metal laminate according to the present embodiment, it ispreferable that the rubber layer have a hardness in accordance with JISK6253 of 60 or more and 100 or less, it is more preferable that it be 70or more and 95 or less, and it is further preferable that it be 80 ormore and 90 or less, from the viewpoint of the appropriate elasticmodulus obtained without exceedingly increasing the hardness of therubber layer to improve the sealability of the sealing targets memberwith preventing deterioration of the sealability.

It is preferable that the rubber-metal laminate according to the presentembodiment have a tensile strength measured in accordance with JIS K6251of 7.5 MPa or more and 30 MPa or less, it is more preferable that it be10 MPa or more and 27.5 MPa or less, and it is further preferable thatit be 12 MPa or more and 25 MPa or less, from the viewpoint ofimprovement in the sealability of the sealing target members withpreventing the protrusion of the rubber layer upon application of thecompressive stress.

The rubber layer can be obtained by using various rubber materialswithin a range that provides the effect of the present invention. As therubber material, various rubber materials such as, for example, anitrile rubber which is an acrylonitrile-butadiene copolymer (NitrileButadiene Rubber: NBR), a hydrogenated nitrile rubber in which theunsaturated bond portion of the nitrile rubber is hydrogenated (HNBR),and a fluorinated rubber can be mentioned. Among them, the nitrilerubber and the hydrogenated nitrile rubber are preferable, and thenitrile rubber is more preferable, from the viewpoint of prevention ofthe protrusion of the rubber layer from the rubber-metal laminate andimprovement in the sealability. When the rubber layer is used forvarious gaskets such as a cylinder head gasket for automobiles, it ispreferable that the rubber layer contain at least one rubber selectedfrom the group consisting of the fluorinated rubber and the nitrilerubber, and it is preferable that the rubber layer contain the nitrilerubber. With the rubber layer containing the nitrile rubber, the nitrilerubber contained in the rubber layer has appropriate elasticity.Therefore, the protrusion of the rubber layer from the rubber-metallaminate can be further prevented even when the compressive stress isapplied to the rubber-metal laminate, and the sealability of the sealingtarget members is further improved. By crosslinking the rubber layer,more excellent heat resistance and adhesiveness are obtained.

In the nitrile rubber, it is preferable that a bound acrylonitrilecontent be 18% or more and 48% or less, it is more preferable that it be31% or more and 42% or less, and it is further preferable that thenitrile rubber be particularly a medium high nitrile having a boundacrylonitrile content of 31% or more and less than 36%, from theviewpoint of improvement in the adhesiveness between the rubber layerand the adhesive and the viewpoint of improvement in cold resistance. Itis preferable that the nitrile rubber have a Mooney viscosity ML1+4(100° C.) of 30 or more and 85 or less from the viewpoint of improvementin friction resistance and abrasion characteristics and the viewpoint ofimprovement in kneading processability, and an acrylonitrile-butadienecopolymer rubber having the Mooney viscosity of 40 or more and 70 orless is used. As the nitrile rubber, commercial products such as tradename “Nipol® DN3350”, manufactured by Zeon Corporation, may be used.

It is preferable that the rubber layer be formed by using a rubbercomposition containing carbon black from the viewpoint of increase inthe hardness of the rubber layer to prevent the protrusion of the rubberlayer from the rubber-metal laminate when the compressive stress isapplied to the rubber-metal laminate.

As the carbon black, hard carbons such as Super Abrasion Furnace (SAF)carbon black, Intermediate Super Abrasion Furnace (ISAF) carbon black,High Abrasion Furnace (HAF) carbon black, and Easy Processing Channel(EPC) carbon black; and soft carbon blacks such as eXtra ConductiveFurnace (XCF) carbon black, Fast Extruding Furnace (FEF) carbon black,General Purpose Furnace (GPF) carbon black, High Modulus Furnace (HMF)carbon black, Semi-Reinforcing Furnace (SRF) carbon black, Fine Thermal(FT) carbon black, and Medium Thermal (MT) carbon black can bementioned. These carbon blacks may be used singly, or may be used incombination of two or more thereof. Among them, the soft carbons arepreferable as the carbon black, and among the soft carbons, theSemi-Reinforcing Furnace carbon black and the Medium Thermal carbonblack are preferable. As the carbon black, commercial products of theMedium Thermal carbon black such as trade name “THERMAX® N990 LSR”(manufactured by Cancarb Ltd.) may be used, and commercial products ofthe Semi-Reinforcing Furnace carbon black such as trade name “HTC #SS”(manufactured by NIPPON STEEL Carbon Co., Ltd.) and trade name “ASAHI#50HG” (manufactured by Asahi Carbon Co., Ltd.) may be used.

It is preferable that a blending amount of the carbon black be 50 partsby mass or more and 500 parts by mass or less, it is more preferablethat it be 70 parts by mass or more and 350 parts by mass or less, andit is further preferable that it be 85 parts by mass or more and 250parts by mass or less, per 100 parts by mass of the rubber componentfrom the viewpoint of prevention of the protrusion of the rubber layerfrom the rubber-metal laminate upon application of the compressivestress to improve the sealability.

It is preferable that the blending amount of the carbon black be 30 mass% or more and 80 mass % or less, it is more preferable that it be 40mass % or more and 70 mass % or less, and it is further preferable thatit be 50 mass % or more and 60 mass % or less, based on the total massof the rubber composition (rubber layer) from the viewpoint ofprevention of the protrusion of the rubber layer from the rubber-metallaminate upon application of the compressive stress to improve thesealability. With the rubber layer containing 30 mass % or more of thecarbon black based on the total mass of the rubber layer, therubber-metal laminate can prevent deterioration of the sealability andachieve an elastic modulus required for the rubber layer. As a result,even when the compressive stress is applied to the rubber-metallaminate, the protrusion of the rubber layer from the rubber-metallaminate can be further prevented, and the sealability of the sealingtarget members can be further improved.

When the carbon black is the MT carbon, it is preferable that theblending amount of the carbon black be 50 parts by mass or more and 300parts by mass or less, it is more preferable that it be 70 parts by massor more and 250 parts by mass or less, and it is further preferable thatit be 85 parts by mass or more and 200 parts by mass or less, per 100parts by mass of the rubber component from the viewpoint of preventionof the protrusion of the rubber layer from the rubber-metal laminateupon application of the compressive stress to improve the sealability.

When the carbon black is the MT carbon, it is preferable that theblending amount of the carbon black be 45 mass % or more and 80 mass %or less, it is more preferable that it be 50 mass % or more and 70 mass% or less, and it is further preferable that it be 55 mass % or more and60 mass % or less, based on the total mass of the rubber compositionfrom the viewpoint of prevention of the protrusion of the rubber layerfrom the rubber-metal laminate upon application of the compressivestress to improve the sealability.

When the carbon black is the SRF carbon, it is preferable that theblending amount of the carbon black be 45 parts by mass or more and 150parts by mass or less, and it is more preferable that it be 50 parts bymass or more and 125 parts by mass or less, per 100 parts by mass of therubber component from the viewpoint of prevention of the protrusion ofthe rubber layer from the rubber-metal laminate upon application of thecompressive stress to improve the sealability.

When the carbon black is the SRF carbon, it is preferable that theblending amount of the carbon black be 30 mass % or more and 70 mass %or less, it is more preferable that it be 35 mass % or more and 65 mass% or less, and it is further preferable it be 40 mass % or more and 60mass % or less, based on the total mass of the rubber composition fromthe viewpoint of prevention of the protrusion of the rubber layer fromthe rubber-metal laminate upon application of the compressive stress toimprove the sealability.

The rubber layer is provided by applying the rubber composition onto themetal member or the primer layer, and then crosslinking the rubbercomposition. It is preferable that the rubber composition contain avulcanizer or a vulcanizing accelerator. As the vulcanizer, commercialproducts such as COLLOIDAL SULFUR A (manufactured by Tsurumi ChemicalIndustry Co., Ltd.) and trade name “Vulnoc® R” (4,4′-dithiodimorpholine:manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) may be used,for example. A blending amount of the vulcanizer is, for example, 0.1part by mass or more and 10 parts by mass or less per 100 parts by massof the rubber component.

As the vulcanizing accelerator, various sulfur-containing vulcanizingaccelerators such as guanidine-type, aldehyde-amine-type,aldehyde-ammonia-type, thiazole-type, sulfenamide-type, thiourea-type,thiuram-type, dithiocarbamate-type, and xanthate-type vulcanizingaccelerators are used. Among them, as the sulfur-containing vulcanizingaccelerator, tetramethylthiuram disulfide, tetrabenzylthiuram disulfide,N-cyclohexyl-2-benzothiazylsulfenamide, and the like are preferable. Asthe vulcanizing accelerator, commercial products such as trade name“Nocceler® TBZTD” (tetrabenzylthiuram disulfide, manufactured by OUCHISHINKO CHEMICAL INDUSTRIAL CO., LTD.), trade name “Nocceler® CZ-P”(N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by OUCHI SHINKOCHEMICAL INDUSTRIAL CO., LTD.), and “Nocceler® TT-P” (tetramethylthiuramdisulfide, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.)may be used. A blending amount of the vulcanizing accelerator is, forexample, 1 part by mass or more and 20 parts by mass or less per 100parts by mass of the rubber component.

The rubber composition may contain fillers such as calcium carbonate andsilica, if necessary. As the calcium carbonate, various calciumcarbonates such as heavy calcium carbonate and synthesized calciumcarbonate can be used. As the calcium carbonate, commercial productssuch as trade name “Whiton SB-Red” (heavy calcium carbonate,manufactured by BIHOKU FUNKA KOGYO CO., LTD.) may be used. It ispreferable that a blending amount of the calcium carbonate be, forexample, 10 parts by mass or more and 100 parts by mass or less per 100parts by mass of the rubber component.

As the silica, various silicas may be used within a range that providesthe effect of the present invention. As the silica, amorphous silicassuch as: silica with dry method manufactured with a pyrolysis methodwith a halogenated silicic acid or an organic silicon compound, a methodof air-oxidizing silicon oxide (SiO) vaporized by heat-reducing silicasand, and the like; and silica with wet method manufactured withpyrolysis method with sodium silicate and the like may be used. As thesilica, commercial products such as trade name “Nipsil® E-74P”(manufactured by TOSOH SILICA CORPORATION) may be used. It is preferablethat a blending amount of the silica be, for example, 5 parts by mass ormore and 50 parts by mass or less per 100 parts by mass of the rubbercomponent.

The rubber composition may contain auxiliaries commonly used in therubber industry such as a plasticizer, an acid acceptor such as zincoxide, stearic acid, an antioxidant, and wax if necessary. As theplasticizer, commercial products such as trade name “ADK CIZER® RS107”(manufactured by ADEKA Corporation) can be mentioned, for example. Ablending amount of the plasticizer is, for example, 1 part by mass ormore and 50 parts by mass or less per 100 parts by mass of the rubbercomponent.

As the acid acceptor, commercial products such as zinc oxide(manufactured by SEIDO CHEMICAL INDUSTRY CO., LTD.) may be used, forexample. As the stearic acid, commercial products such as trade name“DTST” (manufactured by MIYOSHI OIL & FAT CO., LTD.) may be used, forexample. As the antioxidant, commercial products such as trade name“Nocrac® 810-NA” (2,2,4-trimethyl-1,2-dihydroquinoline polymer:manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) may be used,for example. As the wax, commercial products such as trade name“SUNTIGHT® R” (microcrystalline wax: manufactured by Seiko Chemical Co.,Ltd.) may be used, for example.

In the rubber-metal laminate according to the present embodiment, therubber layer has a thickness of 80 μm or more. According to thisthickness, a relationship between the 100%-modulus value and thicknessof the rubber layer is within an appropriate range, and thereby theprotrusion of the rubber layer from the rubber-metal laminate can befurther prevented even when the compressive stress is applied to therubber-metal laminate, and the sealability of the sealing target memberscan be further improved.

It is preferable that the thickness of the rubber layer be 200 μm orless, it is more preferable that it be 90 μm or more and 150 μm or less,and it is further preferable that it be 100 μm or more and 140 μm orless, from the viewpoint of further improvement in the above effect.According to the thickness of the rubber layer of 200 μm or less, in therubber-metal laminate, the relationship between the 100%-modulus valueand thickness of the rubber layer is within an appropriate range, andthe elastic modulus of the rubber layer is further improved. As aresult, the protrusion of the rubber layer from the rubber-metallaminate can be further prevented even when the compressive stress isapplied to the rubber-metal laminate, and the sealability of the sealingtarget members can be further improved.

<Method of Manufacturing Rubber-Metal Laminate>

The rubber-metal laminate according to the above embodiment ismanufactured by using: the metal member such as a stainless steel sheet;and the rubber composition kneaded with a kneading machine such as anintermix, a kneader, and a Banbury mixer, or an open roll to which therubber component and carbon black are blended, and the vulcanizer, thevulcanizing accelerator, calcium carbonate, silica, the plasticizer, andvarious auxiliaries are blended if necessary. The rubber-metal laminateis manufactured by applying the above rubber composition onto a metalmember which has been subjected to the surface treatment if necessary,with the adhesive layer disposed therebetween; and then vulcanizing therubber composition under a condition, for example, at 160° C. or higherand 250° C. or lower for approximately 0.5 minutes or longer and 30minutes or shorter to form the rubber layer. It is preferable that therubber composition be applied so that the thickness of the rubber layerafter the application is 50 μm or more and 200 μm or less. In therubber-metal laminate, coating agents such as a resin-type andgraphite-type coating agent may be applied onto the rubber layer fromthe viewpoint of prevention of adhesion of the rubber.

A method of applying the rubber composition onto the metal member is notparticularly limited as long as it can apply the rubber composition ontothe metal member. As the method of applying the rubber composition, aspraying method, a dipping method, a roll-coating method, a dispensermethod, and the like can be mentioned.

When the rubber composition is manufactured and applied onto the metalmember, the viscosity may be regulated by adding an organic solvent intothe rubber composition, if necessary. The organic solvent is notparticularly limited as long as it can regulate the viscosity of therubber composition to a desired viscosity. As the organic solvent,methyl ethyl ketone, toluene, ethyl acetate, and the like can bementioned, for example. These organic solvents may be used singly, ormay be used in combination of two or more thereof.

As described above, according to the present embodiment, the rubberlayer has a 100%-modulus value of 8.5 MPa or more and a thickness of 80μm or more. As a result, the elastic modulus of the rubber layerappropriately increases. According to this rubber layer, therubber-metal laminate can prevent deterioration of the sealability andachieve an elastic modulus required for the rubber layer compared with acase where the hardness of the rubber layer is increased with a filler.As a result, even when the compressive stress is applied to therubber-metal laminate, the protrusion of the rubber layer from therubber-metal laminate can be further prevented, and the rubber-metallaminate having excellent sealability of the sealing target members canbe achieved. Although the protrusion in the rubber-metal laminate hasbeen conventionally inhibited by simply increasing the hardness of therubber, by performing development with focusing on the 100%-modulusvalue, the protrusion can be inhibited even with a low hardness, and theimprovement in the sealability can be expected. In addition, since theprotrusion of the rubber layer upon application of the compressivestress can be estimated with the 100%-modulus value even withoutactually manufacturing the rubber-metal laminate, it reduces theevaluation process.

According to another embodiment, a gasket including the rubber-metallaminate according to the present embodiment can be obtained. Accordingto the gasket according to the present embodiment, the rubber layer hasa 100%-modulus value of 8.5 MPa or more and a thickness of 80 μm ormore. As a result, the elastic modulus of the rubber layer appropriatelyincreases. According to this rubber layer, the gasket can preventdeterioration of the sealability and achieve an elastic modulus requiredfor the rubber layer compared with a case where the hardness of therubber layer is increased with a filler. As a result, even when thecompressive stress is applied to the gasket, the protrusion of therubber layer from the gasket can be further prevented, and the gaskethaving excellent sealability of the sealing target members can beachieved.

EXAMPLE

Hereinafter, the present invention will be described in more detailbased on Examples performed to clarify the effect of the presentinvention. The present invention is absolutely not limited to thefollowing Examples.

The present inventors produced a rubber-metal laminate according to thepresent embodiment, and performed a compression test on the producedrubber-metal laminate to evaluate it. Hereinafter, the contentsinvestigated by the present inventor will be described.

Example 1 <Evaluation of Thermo Plastics (TP) of Rubber>

Kneading 100 parts by mass of a nitrile rubber (trade name “Nipol®DN3350”, manufactured by Zeon Corporation), 151 parts by mass of acarbon black A (Medium Thermal (MT) carbon black: trade name “THERMAX®N990 LSR”, manufactured by Cancarb Ltd.), 5 parts by mass of zinc oxide(manufactured by SEIDO CHEMICAL INDUSTRY CO., LTD.), 1 part by mass ofstearic acid (trade name “DTST”, manufactured by MIYOSHI OIL & FAT CO.,LTD.), 2 parts by mass of an antioxidant(2,2,4-trimethyl-1,2-dihydroquinoline polymer: trade name “Nocrac®810-NA”, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), 2parts by mass of a microcrystalline wax (trade name “SUNTIGHT® R”,manufactured by Seiko Chemical Co., Ltd.), 1.5 parts by mass of avulcanizer A (COLLOIDAL SULFUR A, manufactured by Tsurumi ChemicalIndustry Co., Ltd.), 1 part by mass of a vulcanizer B(4,4′-dithiodimorpholine: trade name “Vulnoc® R”, manufactured by OUCHISHINKO CHEMICAL INDUSTRIAL CO., LTD.), 5 parts by mass of a vulcanizingaccelerator A (tetrabenzylthiuram disulfide: trade name “Nocceler®TBZTD”, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.), and4 parts by mass of a vulcanizing accelerator B(N-cyclohexyl-2-benzothiazylsulfenamide: trade name “Nocceler® CZ-P”,manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.) wasperformed with a kneader and an open roll to obtain a rubbercomposition. Then, the rubber composition was compressed at 170° C. for8 minutes for vulcanization to produce a rubber sheet having a thicknessof 2 mm. A hardness of the obtained rubber sheet was measured inaccordance with JIS K6253, and a 100%-modulus value, a tensile strength,and an elongation were measured in accordance with JIS K6251.

<Production of Sample for Evaluation of Compression Test>

On a cold rolled steel sheet (SPCC: Steel Plate Cold Commercial)subjected to a surface treatment with a zinc phosphate treating agentand having a thickness of 400 μm, an adhesive in which 100 parts by massof a phenolic resin (97 parts by mass of trade name “Sixon® 715A”,manufactured by Rohm and Haas Company and 3 parts by mass of trade name“Sixon® 715N”, manufactured by Rohm and Haas Company) was diluted withorganic solvents of 440 parts by mass of methyl ethyl ketone and 110parts by mass of methanol was applied so as to have a thickness of 3 μm,and dried at room temperature. Then, the rubber composition having theblending component used in the above Thermo Plastics evaluation wasdissolved in an organic solvent to regulate the viscosity toapproximately 1000 to 10000 mPa·s, and applied onto the cold rolledsteel sheet on which the phenolic resin was applied so that a thicknessof the rubber layer after curing is 120 μm, and then vulcanized with anoven at 200° C. for 3 minutes to produce a sample for evaluation of acompression test of the rubber-metal laminate. Here, anadhesion-preventing layer may be provided if necessary. The producedsample for evaluation of a compression test was evaluated with thefollowing evaluation method. The results are shown in Table 1.

<Evaluation of Compression Test (Protrusion)>

On the rubber layer of the sample for evaluation of a compression testof the rubber-metal laminate, a metal part having a doughnut-likeprotruding shape was pressed under a condition at 100° C. for 5 minutesat a pressure of 150 MPa, and then a state of the rubber layer wasevaluated based on the following criteria.

5 Points: No metal was exposed, and almost no rubber pouring wasobserved.

4 Points: No metal was exposed, and rubber pouring was small.

3 Points: Rubber pouring was not small, but the metal was not exposed.

2 Points: Rubber pouring was large, but metal exposure was small.

1 Point: Both rubber pouring and metal exposure were large.

Example 2

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that 104 parts by mass of a carbon black B (SRF carbon black:trade name “HTC #SS”, manufactured by NIPPON STEEL Carbon Co., Ltd.) wasused instead of the carbon black A. The results are shown in Table 1.

Example 3

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 2except that the thickness of the rubber layer was set to 80 μm. Theresults are shown in Table 1.

Example 4

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 2except that the thickness of the rubber layer was set to 140 μm. Theresults are shown in Table 1.

Example 5

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that 56 parts by mass of a carbon black C (Semi-ReinforcingFurnace (SRF) carbon black: trade name “ASAHI #50HG”, manufactured byAsahi Carbon Co., Ltd.) was used instead of the carbon black A. Theresults are shown in Table 1.

Example 6

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that 90 parts by mass of the carbon black C was used instead ofthe carbon black A. The results are shown in Table 1.

Example 7

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that: the blending amount of the carbon black A was set to 181parts by mass; and 10 parts by mass of a plasticizer (trade name “ADKCIZER® RS107”, manufactured by ADEKA Corporation) was used. The resultsare shown in Table 1.

Example 8

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that: the blending amount of the carbon black A was set to 40parts by mass; 60 parts by mass of the carbon black B was used; 60 partsby mass of calcium carbonate (trade name “Whiton SB-Red”, manufacturedby BIHOKU FUNKA KOGYO CO., LTD.) was used; 30 parts by mass of silica(trade name “Nipsil® E-74P”, manufactured by TOSOH SILICA CORPORATION)was used; and no vulcanizer B was used. The results are shown in Table1.

Comparative Example 1

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that the blending amount of the carbon black A was set to 45parts by mass. The results are shown in Table 1.

Comparative Example 2

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that the blending amount of the carbon black A was set to 90parts by mass. The results are shown in Table 1.

Comparative Example 3

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 2except that the blending amount of the carbon black B was set to 31parts by mass. The results are shown in Table 1.

Comparative Example 4

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 5except that the blending amount of the carbon black C was set to 30parts by mass. The results are shown in Table 1.

Comparative Example 5

A sample for evaluation of a compression test of the rubber-metallaminate was produced to be evaluated in the same manner as in Example 1except that: the blending amount of the carbon black A was set to 60parts by mass; 40 parts by mass of the carbon black B was used; and 60parts by mass of calcium carbonate (trade name “Whiton SB-Red”,manufactured by BIHOKU FUNKA KOGYO CO., LTD.) was used. The results areshown in Table 1.

TABLE 1 Example Comparative Example 1 2 3 4 5 6 7 8 1 2 3 4 5 Thicknessof

120  80  140  120  120 

0

0

0

120 

100 

100  100  100  100 

0 100  100 

100  Carbon black A

181  4

4

0 8

Carbon black B 10

10

0

1

0 Carbon black C

0

0

0

50 

10 

1 1 1 1 1 1 1 1 1 1 1 1 1

 acid 2 2 2 2 2 2 2 2 2 2 2 2 2

2 2 2 2 2 2 2 2 2 2 2 2

 A

 B

 A

 B

Total

100%

 value (MP

)

Elongation (%)

Tensile strength (

)

1 2

indicates data missing or illegible when filed

Details of each component in Table 1 are as follows.

NBR: a nitrile rubber (medium high nitrile (bound acrylonitrile contentof 31% or more and less than 36%): trade name “Nipol® DN3350”,manufacture by Zeon Corporation)

Carbon black A: Medium Thermal (MT) carbon black (trade name “THERMAX®N990 LSR”, manufactured by Cancarb Ltd.)

Carbon black B: Semi-Reinforcing Furnace (SRF) carbon black (trade name“HTC #SS”, manufactured by NIPPON STEEL Carbon Co., Ltd.)

Carbon black C: SRF carbon black (trade name “ASAHI #50HG”, manufacturedby Asahi Carbon Co., Ltd.)

Calcium carbonate: trade name “Whiton SB-Red” (manufactured by BIHOKUFUNKA KOGYO CO., LTD.)

Silica: trade name “Nipsil® E-74P” (manufactured by TOSOH SILICACORPORATION)

Plasticizer: trade name “ADK CIZER® RS107” (manufactured by ADEKACorporation)

Zinc oxide: (manufactured by SEIDO CHEMICAL INDUSTRY CO., LTD.)

Stearic acid: trade name “DTST” (manufactured by MIYOSHI OIL & FAT CO.,LTD.)

Antioxidant: 2,2,4-trimethyl-1,2-dihydroquinoline polymer (trade name“Nocrac® 810-NA”, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO.,LTD.)

Wax: microcrystalline wax (trade name “SUNTIGHT® R”, manufactured bySeiko Chemical Co., Ltd.)

Vulcanizer A: COLLOIDAL SULFUR A (manufactured by Tsurumi ChemicalIndustry Co., Ltd.)

Vulcanizer B: 4,4′-dithiodimorpholine (trade name “Vulnoc® R”,manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO., LTD.)

Vulcanizing accelerator A: tetrabenzylthiuram disulfide (trade name“Nocceler® TBZTD”, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIAL CO.,LTD.)

Vulcanizing accelerator B: N-cyclohexyl-2-benzothiazylsulfenamide (tradename “Nocceler® CZ-P”, manufactured by OUCHI SHINKO CHEMICAL INDUSTRIALCO., LTD.)

As found from Table 1, with the rubber-metal laminate according to thepresent embodiment, since the 100%-modulus value of the rubber layer was8.5 MPa or more, pouring of the rubber in the compression test wasrelatively small, and any of the scores of the protrusion evaluation was4 points or higher (Examples 1 to 8). On the carbon black, using any ofthe Medium Thermal carbon black and the Semi-Reinforcing Furnace carbonblack, the protrusion scores were 4 points or higher (Examples 1 to 6).Even when the thickness of the rubber layer was changed to 80 μm, almostno pouring of the rubber in the compression test was observed, and thescore of the protrusion evaluation was 5 points (Example 3). Inaddition, even when the thickness of the rubber layer was changed to 140μm, almost no pouring of the rubber in the compression test wasobserved, and the score of the protrusion evaluation was 5 points(Example 4). Also, in a case of blending the plasticizer, with the100%-modulus value of the rubber layer being 8.5 MPa or more, almost nopouring of the rubber in the compression test was observed, and thescore of the protrusion evaluation was 5 points (Example 7).Furthermore, in a case of blending calcium carbonate and silica, thepouring of the rubber in the compression test was relatively small whenthe 100%-modulus value of the rubber layer was 8.5 MPa or more, and thescore of the protrusion evaluation was 4 points (Example 8).

In contrast, any of cases where the 100%-modulus value of the rubberlayer is less than 8.5 MPa, it is found that the pouring of the rubberin the compression test is large, and the scores of the protrusionevaluation are 1 point to 3 points (Comparative Examples 1 to 5).

From the above results, it is found that, according to the presentembodiment, by setting the 100%-modulus value of the rubber layer to 8.5MPa or more and the thickness of the rubber layer to 80 μm or more, theprotrusion of the rubber layer can be prevented even when thecompressive stress is applied to the rubber-metal laminate, and thesealability of the rubber-metal laminate is improved.

INDUSTRIAL APPLICABILITY

As described above, the present embodiment has the effect of achievingthe rubber-metal laminate and gasket that can prevent the protrusion ofthe rubber layer upon application of the compressive stress and that hasexcellent sealability of the sealing target members. The rubber-metallaminate and the gasket according to the present embodiment can bepreferably used for, particularly, various gaskets such as a cylinderhead gasket, and the like. In addition, such a rubber-metal laminate canalso be used for, as uses other than the gasket, compressors, waterpumps, motors, batteries, power control units, inverter cases, and thelike.

One embodiment of the present invention has been described above;however, embodiments of the present invention are not limited by thecontents of the present embodiment. In addition, components that aperson skilled in the art can easily anticipate and components that issubstantially same, a so-called equivalent range, are included in theabove component. In addition, the above component can be appropriatelycombined. Furthermore, within a range not impairing the spirit of theabove embodiment, omission, substitution, or modification of each of thecomponent can be made.

1. A rubber-metal laminate, characterized by comprising: a metal member; and a rubber layer provided on the metal member, wherein the rubber layer has a 100%-modulus value in accordance with JIS K6251 of 8.5 MPa or more and a thickness of 80 μm or more and 200 μm or less, and the rubber layer contains 40 mass % or more of carbon black based on a total mass of the rubber layer.
 2. The rubber-metal laminate according to claim 1, wherein the rubber layer has a 100%-modulus value in accordance with JIS K6251 of 10.5 MPa or more.
 3. The rubber-metal laminate according to claim 1, wherein the rubber layer has an elongation value in accordance with JIS K6251 of 100% or more. 4-5. (canceled)
 6. The rubber-metal laminate according to claim 1, wherein the metal member and the rubber layer are bonded with at least one adhesive selected from the group consisting of a phenolic resin and an epoxy resin disposed therebetween.
 7. The rubber-metal laminate according to claim 1, wherein the rubber layer contains a nitrile rubber.
 8. A gasket, comprising the rubber-metal laminate according to claim
 1. 